CN119425668A - A rare earth manganese zirconium composite catalytic material and preparation method thereof, and catalyst - Google Patents
A rare earth manganese zirconium composite catalytic material and preparation method thereof, and catalyst Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 139
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 80
- DSGIMNDXYTYOBX-UHFFFAOYSA-N manganese zirconium Chemical compound [Mn].[Zr] DSGIMNDXYTYOBX-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 118
- 239000011572 manganese Substances 0.000 claims abstract description 62
- -1 rare earth zirconium oxide Chemical class 0.000 claims abstract description 55
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 43
- 150000001450 anions Chemical class 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 18
- 150000001768 cations Chemical class 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910002651 NO3 Inorganic materials 0.000 claims description 18
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 150000002697 manganese compounds Chemical class 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 150000003755 zirconium compounds Chemical class 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 235000013877 carbamide Nutrition 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 3
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000010815 organic waste Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 2
- 125000002091 cationic group Chemical group 0.000 claims 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 229910052693 Europium Inorganic materials 0.000 claims 1
- 229910052688 Gadolinium Inorganic materials 0.000 claims 1
- 229910052779 Neodymium Inorganic materials 0.000 claims 1
- 229910052777 Praseodymium Inorganic materials 0.000 claims 1
- 229910052769 Ytterbium Inorganic materials 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 8
- 229910052863 mullite Inorganic materials 0.000 description 8
- 230000033116 oxidation-reduction process Effects 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
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- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a rare earth manganese zirconium composite catalytic material and a preparation method thereof, and a catalyst, wherein the rare earth manganese zirconium composite catalytic material comprises crystalline rare earth zirconium oxide and amorphous manganese oxide, the chemical general formula of the rare earth manganese zirconium oxide is RE aMnbZrcLdO(2‑δ)Dβ, RE is rare earth element, L is cation doping element, and D is anion doping element, wherein a is more than or equal to 0.10 and less than or equal to 0.85,0.05, b is more than or equal to 0.25,0.10 and less than or equal to c is more than or equal to 0.85, D is more than or equal to 0 and less than or equal to 0.20, delta is more than or equal to 0 and less than or equal to 0.30,0 and beta is more than or equal to 0.10, and d=1-a-b-c. The interaction of the manganese oxide and the rare earth zirconium-based oxide is utilized to enhance the dispersibility of active manganese, improve the utilization rate of manganese atoms, and increase the concentration of oxygen defects, so that the quantity of active oxygen is increased, the active oxygen has high catalytic activity on NO at low temperature and higher durability, the use amount of platinum group metals is reduced, and the oxidation rate of NO is improved.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a rare earth manganese zirconium composite catalytic material, a preparation method thereof and a catalyst.
Background
The diesel engine exhaust contains a large amount of nitrogen oxides (NOx), hydrocarbon (HCs) and particulate matters PM, so that not only can the human respiratory system be seriously damaged, but also the atmospheric pollution can be caused, and along with the increasing of emission regulations, how to effectively remove NOx, HCs, PM in the engine exhaust becomes a research hot spot for the catalysis of the current environment. The existing stage of diesel engine tail gas aftertreatment mainly comprises an oxidation catalyst (DOC), a Selective Catalyst (SCR), a particle trap (DPF), an Ammonia Slip Catalyst (ASC) and the like. Wherein DOC is critical for NOx, HCs, and PM removal.
The DOC (i.e. diesel oxidation catalyst) is centered on its coating material, which carries the critical catalytic task of efficiently converting NO to NO2, and the DOC catalyst usually employs noble metal-supported alumina as the active ingredient. At present, the noble metal dosage of the DOC catalyst is usually more than 25g/ft3, the cost is higher, and simultaneously, as the global emission regulations are continuously tightened, more stringent requirements are put on the performance of the DOC catalyst. On the one hand, the inlet operating temperature of the catalyst needs to be significantly reduced to accommodate a wider range of operating conditions, and on the other hand, the catalytic efficiency and durability must reach a new level. The catalyst performance can be improved by simply increasing the loading of noble metal, the performance requirement can be met to a certain extent, but the rapid rising of the cost can be caused, and the catalyst is not a sustainable solution.
Disclosure of Invention
The rare earth manganese zirconium composite catalytic material comprises crystalline rare earth zirconium oxide and amorphous manganese oxide, so that the catalyst has higher low-temperature NO oxidation performance, improves durability, has high catalytic activity on NO at low temperature and higher durability, reduces the use amount of platinum group metals, and improves the NO oxidation rate.
In order to solve the technical problems, a first aspect of the embodiment of the invention provides a rare earth manganese zirconium composite catalytic material, which comprises a crystalline rare earth zirconium oxide and an amorphous manganese oxide, wherein the chemical general formula of the rare earth manganese zirconium composite catalytic material is RE aMnbZrcLdO(2-δ)Dβ, RE is a rare earth element, L is a cation doping element, and D is an anion doping element;
Wherein, in terms of mole number, a is more than or equal to 0.10 and less than or equal to 0.85,0.05 and b is more than or equal to 0 0.25,0.10.ltoreq.c.ltoreq.0.85, 0.ltoreq.d.ltoreq. 0.20, 0.ltoreq.delta.ltoreq. 0.30,0.ltoreq.beta.ltoreq.0.10, d=1-a-b-c.
Further, the amorphous manganese oxide comprises at least one of Mn 3O4、Mn2O3、MnO2、REMn2O5 and REMnO 3, preferably at least one of REMn 2O5、Mn3O4 and Mn 2O3.
Further, the crystalline rare earth zirconium oxide comprises a tetragonal phase and/or a cubic phase.
Further, the amorphous manganese oxide is located on the surface and/or grain boundaries of the crystalline rare earth zirconium oxide.
Further, the Mn comprises at least one of Mn 2+、Mn3+ and Mn 4+;
The molar ratio of Mn 4+ to (Mn 2++Mn3+) is in the range of 0.2:1 to 2:1.
Further, the RE includes at least one of La, ce, pr, nd, sm, eu, gd, yb and Y.
Further, the cation doping element L comprises at least one of alkaline earth metal, transition metal, aluminum and silicon element, preferably at least one of Fe, co, ni, cu, zn, V, ti, cr, mo, W, sn, nb, al, si, ga, ge, in, hf, ba, sr, mg and Ca;
The anion doping element D comprises at least one of anions N, P, F and S.
Further, the pore diameter range of the rare earth manganese zirconium composite catalytic material is concentrated in 1 nm-4 nm and 15 nm-25 nm;
The pore volume range of the rare earth manganese zirconium composite catalytic material is 0.2cm 3/g～0.6cm3/g.
Correspondingly, a second aspect of the embodiment of the invention provides a rare earth manganese zirconium composite catalytic material, which is used for preparing the rare earth manganese zirconium composite catalytic material, and comprises the following steps:
S1, mixing all zirconium compounds, part of RE compounds and part of aqueous solutions of L compounds, adding alkaline substances for precipitation reaction, and filtering, washing, drying and roasting to obtain RE-L-containing rare earth zirconium oxide;
S2, mixing all manganese compounds, residual RE compounds and residual L compounds with the rare earth zirconium oxide obtained in the step S1 to obtain a composite compound precursor;
And S3, performing heat treatment on the composite compound precursor obtained in the step S2 to obtain the rare earth manganese zirconium composite catalytic material containing the amorphous manganese oxide.
Correspondingly, a third aspect of the embodiment of the invention provides a rare earth manganese zirconium composite catalytic material, which is used for preparing the rare earth manganese zirconium composite catalytic material, and comprises the following steps:
S1, mixing all zirconium compounds, part of RE compounds and all L compounds in water, adding alkaline substances for precipitation reaction, and filtering, washing, drying and roasting to obtain RE-L-containing rare earth zirconium oxide;
S2, mixing all manganese compounds and residual RE compounds with the rare earth zirconium oxide obtained in the step S1 to obtain a compound precursor;
And S3, performing heat treatment on the composite compound precursor obtained in the step S2 to obtain the rare earth manganese zirconium composite catalytic material containing the amorphous manganese oxide.
Further, the preparation method of the rare earth manganese zirconium composite catalytic material further comprises the following steps:
the compound of the anionic doping element D is added during the precipitation of step S1 and/or during the mixing of step S2.
Further, the manganese compound comprises at least one of chloride, nitrate, sulfate, permanganate and acetate, preferably manganese nitrate;
The zirconium compound comprises at least one of oxychloride, nitrate, sulfate, acetate and citrate, preferably zirconyl nitrate;
the cation doped element L compound and the rare earth element RE compound comprise at least one molten salt or aqueous solution of chloride, nitrate, sulfate, acetate, citrate, amino acid salt and organic silicon compound, preferably nitrate;
The compound of the anion doping element D comprises at least one of nitrate, fluoride, phosphate and sulfate, and preferably, the anion doping element D comprises nitrate and/or sulfate;
The alkaline substance comprises at least one of urea, hydroxide, ammonia water, carbonate and bicarbonate, wherein the bicarbonate comprises at least one of ammonium, potassium, sodium and magnesium, the hydroxide comprises at least one of ammonium, sodium, potassium and magnesium, and the alkaline substance preferably comprises at least one of sodium hydroxide, urea, ammonia water and ammonium bicarbonate.
Further, the pH value range in the precipitation process in the step S1 is 4.5-14, preferably 5-11;
The pH value range of the precipitation end point in the step S1 is 8-13, preferably 9-11;
the temperature in the precipitation process of the step S1 is 5-120 ℃, preferably 20-80 ℃.
Further, the roasting temperature range of the step S1 is 500-1000 ℃, preferably 600-900 ℃;
The heat treatment temperature in the step S3 is 300-900 ℃, preferably 400-800 ℃;
The roasting and heat treatment are performed in a preset atmosphere, wherein the preset atmosphere comprises at least one of air, O 2、CO、CO2 and N 2.
Correspondingly, a fourth aspect of the embodiment of the invention provides a catalyst, which comprises the rare earth manganese zirconium composite catalytic material and is applied to the tail gas purification of motor vehicles, the organic waste gas purification, the flue gas denitration or the catalytic combustion of natural gas.
The technical scheme provided by the embodiment of the invention has the following beneficial technical effects:
1. The rare earth manganese zirconium composite catalytic material comprises crystalline rare earth zirconium oxide and amorphous manganese oxide, so that the NO oxidation performance of the catalyst in a low-temperature environment is improved, the excellent low-temperature catalytic activity is shown, the durability of the catalyst is remarkably enhanced, the long-term high-efficiency catalytic effect is ensured, the requirement on platinum group metals is effectively reduced, the cost saving is realized, and the NO oxidation efficiency is synchronously improved;
2. The rare earth manganese zirconium composite catalytic material containing amorphous manganese oxide utilizes the riveting action of rare earth zirconium oxide in a crystalline phase on the amorphous manganese oxide, is favorable for improving the thermal stability of the amorphous manganese oxide, ensures that the amorphous manganese oxide still maintains an amorphous structure at a high temperature of 800 ℃, has particularly rich active oxygen and defect structure, can be used for rapidly transferring oxygen elements, and improves the oxidation-reduction performance;
3. The rare earth manganese zirconium composite catalytic material comprises crystalline rare earth zirconium oxide and amorphous manganese oxide, wherein the manganese oxide is in amorphous distribution by utilizing the interaction of the manganese oxide and the rare earth zirconium-based oxide, the dispersibility of active manganese is enhanced, the utilization rate of manganese atoms is improved, the concentration of oxygen defects is increased, the quantity of active oxygen is increased, and the catalytic activity of the rare earth manganese zirconium composite catalytic material is improved.
Drawings
FIG. 1 is an XRD pattern of a rare earth manganese zirconium composite catalyst material containing amorphous manganese oxide provided by an embodiment of the present invention.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
The first aspect of the embodiment of the invention provides a rare earth manganese zirconium composite catalytic material, which comprises a crystalline rare earth zirconium oxide and an amorphous manganese oxide, wherein the chemical general formula of the rare earth manganese zirconium composite catalytic material is RE aMnbZrcLdO(2-δ)Dβ, RE is a rare earth element, L is a cation doping element, and D is an anion doping element, wherein a is more than or equal to 0.10 and less than or equal to 0.85,0.05, b is more than or equal to 0.25,0.10 and less than or equal to c is more than or equal to 0.85, D is more than or equal to 0 and less than or equal to 0.20, delta is more than or equal to 0 and less than or equal to 0.30,0 and less than or equal to 0.10, and d=1-a-b-c.
In the technical scheme, the main catalytic activity of the rare earth manganese zirconium composite catalytic material containing the amorphous manganese oxide is concentrated on the amorphous manganese oxide. Compared with crystalline manganese oxide, the amorphous manganese oxide has the characteristics of short-range order and long-range disorder, and the metal ions in the short-range order structure can exert strong interaction of atomic level, so that p-d electron hybridization between Mn and O is enhanced, the manganese element has more abundant valence state, the oxidation-reduction cycle of active Mn 3+/Mn4+ is facilitated, and the oxidation-reduction performance is improved.
The rare earth manganese zirconium composite catalytic material containing amorphous manganese oxide utilizes the riveting action of rare earth zirconium oxide in a crystalline phase on the amorphous manganese oxide, is favorable for improving the thermal stability of the amorphous manganese oxide, ensures that the amorphous manganese oxide still maintains an amorphous structure at a high temperature of 800 ℃, has particularly rich active oxygen and defect structure, and can be used for rapidly transferring oxygen elements and improving the oxidation-reduction performance.
Further, the amorphous manganese oxide comprises at least one of Mn 3O4、Mn2O3、MnO2、REMn2O5 and REMnO 3, preferably at least one of REMn 2O5、Mn3O4 and Mn 2O3.
Further, the crystalline rare earth zirconium oxide comprises a tetragonal phase and/or a cubic phase.
Further, the amorphous manganese oxide is located on the surface and/or grain boundaries of the crystalline rare earth zirconium oxide.
Further, the Mn contains at least one of Mn 2+、Mn3+、Mn4+, and the molar ratio of Mn 4+ to (Mn 2++Mn3+) is in the range of 0.2:1-2:1.
Further, RE includes at least one of La, ce, pr, nd, sm, eu, gd, yb and Y.
Further, the cation doping element L includes at least one of alkaline earth metal, transition metal, aluminum and silicon, preferably at least one of Fe, co, ni, cu, zn, V, ti, cr, mo, W, sn, nb, al, si, ga, ge, in, hf, ba, sr, mg and Ca, and the anion doping element D includes at least one of anions N, P, F and S.
Further, the pore diameter range of the rare earth manganese zirconium composite catalytic material is concentrated at 1 nm-4 nm and 15 nm-25 nm, and the pore volume range of the rare earth manganese zirconium composite catalytic material is 0.2cm 3/g～0.6cm3/g.
In the preparation process of the traditional manganese oxide amorphous phase catalytic material, the calcination temperature and the material use condition need to be controlled, otherwise, the phenomena of crystallization, particle sintering and agglomeration of the manganese oxide can be caused, so that the catalytic activity of the manganese oxide serving as an active component of the catalyst is reduced, the utilization rate of the active component is reduced, and the catalyst has poor long-term stability.
Correspondingly, a second aspect of the embodiment of the invention provides a rare earth manganese zirconium composite catalytic material, which is used for preparing the rare earth manganese zirconium composite catalytic material, and comprises the following steps:
S1, mixing all zirconium compounds, part of RE compounds and part of aqueous solutions of L compounds, adding alkaline substances for precipitation reaction, and filtering, washing, drying and roasting to obtain RE-L-containing rare earth zirconium oxide;
S2, mixing all manganese compounds, residual RE compounds and residual L compounds with the rare earth zirconium oxide obtained in the step S1 to obtain a composite compound precursor;
And S3, performing heat treatment on the composite compound precursor obtained in the step S2 to obtain the rare earth manganese zirconium composite catalytic material containing the amorphous manganese oxide.
Correspondingly, a third aspect of the embodiment of the invention provides a rare earth manganese zirconium composite catalytic material, which is used for preparing the rare earth manganese zirconium composite catalytic material, and comprises the following steps:
S1, mixing all zirconium compounds, part of RE compounds and all L compounds in water, adding alkaline substances for precipitation reaction, and filtering, washing, drying and roasting to obtain RE-L-containing rare earth zirconium oxide;
S2, mixing all manganese compounds and the rest RE compounds with the rare earth zirconium oxide obtained in the step S1 to obtain a compound precursor;
And S3, performing heat treatment on the composite compound precursor obtained in the step S2 to obtain the rare earth manganese zirconium composite catalytic material containing the amorphous manganese oxide.
In both embodiments, the mixing process in step S2 may locate the amorphous manganese oxide at the surface and/or grain boundaries of the crystalline rare earth zirconium oxide.
Further, the preparation method of the rare earth manganese zirconium composite catalytic material also comprises the following steps:
the compound of the anionic doping element D is added during the precipitation of step S1 and/or during the mixing of step S2.
Further, the manganese compound includes at least one of chloride, nitrate, sulfate, permanganate and acetate, preferably manganese nitrate;
the zirconium compound includes at least one of oxychloride, nitrate, sulfate, acetate and citrate, preferably zirconyl nitrate;
the cation doped element L and the rare earth element RE comprise at least one molten salt or aqueous solution of chloride, nitrate, sulfate, acetate, citrate, amino acid salt and organosilicon compound, preferably nitrate;
The compound of the anion doping element D comprises at least one of nitrate, fluoride, phosphate and sulfate, and preferably, the anion doping element D comprises nitrate and/or sulfate;
the alkaline substance comprises at least one of urea, hydroxide, ammonia water, carbonate and bicarbonate, wherein the bicarbonate comprises at least one of ammonium, potassium, sodium and magnesium, the hydroxide comprises at least one of ammonium, sodium, potassium and magnesium, and the alkaline substance preferably comprises at least one of sodium hydroxide, urea, ammonia water and ammonium bicarbonate.
Further, the pH value range in the precipitation process in the step S1 is 4.5-14, preferably 5-11;
The pH value range of the precipitation end point in the step S1 is 8-13, preferably 9-11;
the temperature in the precipitation process of the step S1 is 5-120 ℃, preferably 20-80 ℃.
Further, the roasting temperature in the step S1 ranges from 500 ℃ to 1000 ℃, preferably from 600 ℃ to 900 ℃;
the heat treatment temperature in the step S3 ranges from 300 ℃ to 900 ℃, preferably from 400 ℃ to 800 ℃;
The calcination and the heat treatment are performed in a preset atmosphere including at least one of air, O 2、CO、CO2 and N 2.
The preparation process of the rare earth manganese zirconium composite catalyst material of the amorphous manganese oxide is specifically described below by comparative examples and examples of several preparation methods, wherein the evaluation condition of the catalytic performance is 500ppm of NO,8% of O 2,500ppm CO,300ppm HC,N2 as balance gas, and the space velocity is 80000h -1.
Comparative example 1:
proportioning according to the mole ratio of La/Y/Ce/Zr/Nd in La 0.05Y0.05Ce0.3Zr0.55Nd0.05O2 rare earth zirconium oxide to obtain mixed solution with total cation concentration of 1.5M, adding the mixed solution into 3.0M NaOH solution at uniform speed under stirring, precipitating with pH of 10-14, end point pH of 10 and temperature of 50 ℃, filtering, washing, drying and roasting at 550 ℃ for 8h to obtain tetragonal rare earth zirconium oxide La 0.05Y0.05Ce0.3Zr0.55Nd0.05O2.
The rare earth zirconium oxide obtained by the preparation method of the comparative example 1 has a catalytic oxidation NO conversion rate of 7% at 240 ℃, the highest NO conversion rate of 20%, and the conversion temperature corresponding to the highest conversion rate of 385 ℃.
Comparative example 2:
Proportioning according to the molar ratio of Y/Mn in YMn 2O5 rare earth manganese oxide to obtain a mixed solution with the total concentration of cations being 1.2M, adding the mixed solution and a 2.8M NaOH solution into a reactor at uniform speed under the stirring condition, precipitating to obtain a pH value of 9+/-0.2, controlling the end point pH value to be 9 and the temperature to be 40 ℃, adding H 2O2 with the molar amount equal to Mn 2+, filtering, washing and drying the precipitate, and roasting at 820 ℃ for 8 hours to obtain the molar ratio of YMn 2O5.Mn4+ and (Mn 2++Mn3+) rare earth manganese oxide of mullite phase being 0.2:1.
The mullite phase rare earth manganese oxide obtained by the preparation method of the comparative example 2 has the NO conversion rate of 10% in the catalytic oxidation at 240 ℃, the highest NO conversion rate is 45%, and the conversion temperature corresponding to the highest conversion rate is 366 ℃.
Comparative example 3:
Mixing Sm/Zr/Y in a rare earth manganese zirconium composite catalytic material of Sm 0.12Mn0.35Zr0.4Y0.13O1.98 according to a molar ratio of 3:40:4 to obtain a mixed solution with total cation concentration of 1.0M, adding the mixed solution into 2.0M ammonia water solution at uniform speed under the condition of stirring, precipitating at pH of 5-9 and end pH of 8.9 at a temperature of 60 ℃, filtering, washing and drying the precipitate, and roasting at 830 ℃ for 8 hours to obtain the tetragonal phase rare earth zirconium oxide. The rare earth zirconium oxide is mixed with 1.8M Mn (NO 3)2 solution containing Sm and Y) and then is heat treated for 13 hours in the air at 900 ℃ to obtain the rare earth manganese zirconium composite catalytic material containing tetragonal phase and mullite phase, wherein the tetragonal phase accounts for 82 percent, the mullite phase accounts for 18 percent, and the mole ratio of Mn 4+ to (Mn 2++Mn3+) is 0.3:1.
The rare earth manganese oxide containing tetragonal phase and mullite phase obtained by the preparation method of the comparative example 3 has the NO conversion rate of 13% in the catalytic oxidation at 240 ℃, the highest NO conversion rate is 50%, and the conversion temperature corresponding to the highest conversion rate is 360 ℃.
Comparative example 4:
The preparation method comprises the steps of preparing a mixed solution with the total concentration of cations of 1.0M according to the molar ratio of Ce/Zr/Y in the Ce 0.27Mn0.43Zr0.15Y0.15O1.98 rare earth manganese zirconium composite catalytic material of 27:20:3, adding the mixed solution into a 2.0M NaOH solution at uniform speed under the condition of stirring, precipitating at pH of 6-10 and end pH of 9.8 at 40 ℃, filtering, washing and drying the precipitate, and roasting at 600 ℃ for 4 hours to obtain cubic phase rare earth zirconium oxide. The rare earth zirconium oxide is mixed with 1.2M Mn (NO 3)2 solution) containing Y and then is heat treated for 13 hours in air at 700 ℃ to obtain the rare earth manganese zirconium composite catalytic material containing cubic phase, mullite phase and Mn3O4 phase, wherein the cubic phase accounts for 77 percent, the mullite phase accounts for 20 percent, and the Mn 3O4 phase accounts for 3 percent, and the mole ratio of Mn 4+ to (Mn 2++Mn3+) is 0.3:1.
The rare earth manganese oxide containing tetragonal phase and mullite phase obtained by the preparation method of the comparative example 3 has the conversion rate of 14% in the catalytic oxidation of NO at 240 ℃, the highest conversion rate of 52% of NO and the corresponding conversion temperature of 359 ℃.
Example 1
The preparation method comprises the steps of preparing a mixed solution with the concentration of 1.5M by dissolving Ce/La/Y/Zr in a Ce 0.06La0.05Y0.08Mn0.21Zr0.6O1.94 rare earth manganese zirconium composite catalytic material with water according to the mol ratio of 6:2:3:60, adding the mixed solution into a 2.1M NaOH solution at uniform speed under the stirring condition, precipitating at the pH of 10-14 and the end pH of 10 at the temperature of 50 ℃, filtering, washing and drying the precipitate, and roasting the dried product at 800 ℃ for 7 hours to obtain the tetragonal phase rare earth zirconium oxide. Rare earth zirconium oxide was mixed with 1.2M Mn (NO 3)2) solution containing La and Y, then heat treated at 150℃for 5 hours in an oxygen atmosphere, and then calcined at 500℃for 12 hours in an air atmosphere to give an amorphous manganese oxide having a molar ratio of Mn 4+ to (Mn 2++Mn3+) of 0.5:1, containing REMn 2O5、Mn3O4, and having a pore volume of 0.3cm 3/g.
The rare earth manganese zirconium composite catalytic material containing amorphous manganese oxide obtained by the preparation method of the embodiment of the invention has the catalytic oxidation NO conversion rate of 37 percent at 240 ℃, the highest NO conversion rate of 70 percent and the conversion temperature corresponding to the highest conversion rate of 298 ℃.
Examples 2-43 were conducted in the same manner as in example 1 except that it was noted below. The specific phase structure compositions and performance test results of the examples are shown in table 1.
Specifically, the molar ratio of Mn 4+ to (Mn 2++Mn3+) was measured using XPS. Through Gaussian fitting peak splitting on a spectrum peak of Mn 2p, in an XPS spectrogram, a peak signal of which the electron binding energy is near 640eV is attributed to divalent Mn (Mn 2+), a peak signal of which the electron binding energy is near 641.3eV is attributed to trivalent Mn (Mn 3+), a characteristic signal of tetravalent Mn (Mn 4+) is near 642.5eV, and a molar ratio of Mn 4+ to (Mn 2++Mn3+) is calculated through a ratio of a corresponding peak area of Mn 4+ to a corresponding peak area of Mn 2+、Mn3+. And analyzing the amorphous manganese oxide species by synchrotron radiation by XRD analyte phase composition.
Table 1 comparative and example phase structure compositions and performance test results
Referring to table 1, it can be seen from the disclosure in table 1 that by adjusting the types, the sequences and the proportions of the manganese compound, the RE compound and the L compound, and adjusting the test conditions such as the atmosphere and the temperature in the preparation process, the rare earth manganese zirconium composite catalytic material with the chemical formula RE aMnbZrcLdO(2-δ)Dβ can be prepared, wherein the rare earth manganese zirconium composite catalytic material comprises crystalline rare earth zirconium oxide and amorphous manganese oxide, RE is a rare earth element, L is a cation doping element, and D is an anion doping element.
Figure 1 analyzes the XRD structure of the rare earth manganese zirconium composite catalytic material, and its phase only contains the tetragonal phase of rare earth zirconium oxide, and no manganese oxide phase is detected, indicating successful synthesis of amorphous rare earth manganese zirconium composite catalytic material.
Correspondingly, a fourth aspect of the embodiment of the invention provides a catalyst, which comprises the rare earth manganese zirconium composite catalytic material and is applied to the tail gas purification of motor vehicles, the organic waste gas purification, the flue gas denitration or the catalytic combustion of natural gas.
The catalyst based on the rare earth manganese zirconium composite catalytic material can be used for efficiently removing pollutants such as CO, HC and soot in automobile exhaust, is beneficial to the catalytic oxidation of NO into NO 2, improves the low-temperature activity of the motor vehicle exhaust purification catalyst, and reduces the consumption of noble metals in the catalyst.
The embodiment of the invention aims to protect a rare earth manganese zirconium composite catalytic material, a preparation method thereof and a catalyst, wherein the rare earth manganese zirconium composite catalytic material comprises crystalline rare earth zirconium oxide and amorphous manganese oxide, the chemical general formula of the rare earth manganese zirconium oxide is RE aMnbZrcLdO(2-δ)Dβ, RE is a rare earth element, L is a cation doping element, and D is an anion doping element, wherein a is more than or equal to 0.10 and less than or equal to 0.85,0.05, b is more than or equal to 0.25,0.10 and less than or equal to c is more than or equal to 0.85, D is more than or equal to 0 and less than or equal to 0.20, delta is more than or equal to 0 and less than or equal to 0.30,0 and beta is less than or equal to 0.10, and d=1-a-b-c. The technical scheme has the following effects:
1. the rare earth manganese zirconium composite catalytic material contains crystalline rare earth zirconium oxide and amorphous manganese oxide, so that the catalyst has higher low-temperature NO oxidation performance, improves the durability, has high catalytic activity on NO at low temperature and higher durability, reduces the use amount of platinum group metals, and improves the NO oxidation rate;
2. The rare earth manganese zirconium composite catalytic material containing amorphous manganese oxide utilizes the riveting action of rare earth zirconium oxide in a crystalline phase on the amorphous manganese oxide, is favorable for improving the thermal stability of the amorphous manganese oxide, ensures that the amorphous manganese oxide still maintains an amorphous structure at a high temperature of 800 ℃, has particularly rich active oxygen and defect structure, can be used for rapidly transferring oxygen elements, and improves the oxidation-reduction performance;
3. The rare earth manganese zirconium composite catalytic material comprises crystalline rare earth zirconium oxide and amorphous manganese oxide, wherein the manganese oxide is in amorphous distribution by utilizing the interaction of the manganese oxide and the rare earth zirconium-based oxide, the dispersibility of active manganese is enhanced, the utilization rate of manganese atoms is improved, the concentration of oxygen defects is increased, the quantity of active oxygen is increased, and the catalytic activity of the rare earth manganese zirconium composite catalytic material is improved.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
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